Brown trisazo dyestuffs and process of making same



Patented Dec; 15,1925.

UNITED, STATES PATENT OFFICE.

BAnTHoLoMAUs vossEN, 0F nocnsm-on-mnn mim, GERMANY, Assxcnon, BY MESNE ASSIGNMENTS, T0 GRASSELLI DYESTUFF CORPORATION, on NEW YORK, N. Y., A

CORPORATION OF DELAWARE.

BROWN TRISAZO DYESTUFFS AND PROCESS OF MAKING SAME.

No Drawin.

To all whom it may concern:

Be it known that I, BARTHOLoMKUS Vos- SEN, a citizen of Germany, residing at Hochst-on-the-Main, Germany, have invented certain new and useful Improvements in Brown Trisazo Dyestufls and Processes of Making Same, of which the following is a specification. v

The only Way for obtaining by means of acid azodyestufl's deep reddish to olivebrown dyeings on leather prepared by the various tanning-processes ms hitherto, in almost all cases, been to attain the desired tints bymixing several dyestuits. It is a' well known fact that such dyestuif-mixtures entail various drawbacks because the several dyestuffs have as a rule a different aflinity for the material to be dyed so that they are apt to give uneven dyeings; moreover when using mixtures it is very difficult to secure always one and the same tint. "In particular no deep-brown dyestufi for dyeing leather has hitherto been known which constituted a uniform chemicalbody and conse quently did not show the disadvantages of the dyestufi-mixtures. 1

Now I have found that valuable, uniform brown dyestuffs especially adapted for leath er-dyeing are obtained by preparing monoazodyestufi's: from diazotized amines or'their substitution products with resorcinol or its substitution products, especially chloro-resorcine, 1.3.4-resorcylic acid or the like and then coupling with a diazotized aminonaphs thol or its substitution products and finally causing diazotized amines or their substitution products to act upon them.

The synthesis of the dyestuffs in question may be explained by the following scheme:

(1) o) amine resorcinol aminonaphthol amine or naphthalene series, and by aminophenols Application filed December 17, 1924. Serial No. 756,550.

sulfonic acid or the like and in the final posi- 7 tion (4) unsulfonated nitroor halogensubstituted arylamines. By a suitable selection of the several components in the abovestated scheme the most varied shades, from olive-brown to reddish-brown, may be obtained.

The dyestuffs-possess excellent properties as to fastncss, particularly an ex cellent fastness to light, they give even tints, are also readily soluble and the dye-bath is ex-" hausted. very well. The tints obtainable thereby are of surprising beauty.

The following examples illustrate my invention: I

1. Dario-brown for leather.

17,3 kilos of sulfanilic acid are diazotized in the usual manner and coupled with 11,0 kilos of resorcinol dissolved with 8,0 kilos of caustic soda solution. The whole is stirred'for 5 hours and then there is slowly added in the usual manner the diazo compound from 23,9 kilos of 1-amino-8-naphthol-4-sulphonic acid. After the coupling is finished the acetic acid diazo compound of 13,8 kilos" of l-llitIO-l-dlilZObGIlZGll is added tothe diazodyestufl. After the coupling is complete, the dyestuff is salted out in the usual manner.

Thus there is. obtained witha good yield a dyestufi which Na 5 ON:

Similar valuable dyestufis are obtained by substituting for the sulfanilic acid the 6- I givescon chrome leather, a yellowish dark-brown tint. or on leather tanned with a Vegetable agent,

has the following formula:

5 Game 11,0 kilos of resorcinol dissolved with 8,0 kilos of caustic soda solution. The

The dvestufi' chloro-Q-toluidinel-sulfonic acid, 6-chloro1 mass is stirred for 5 hours and there are 3-toluidinel-sulfonic acid or one of their then added in the usual manner 5 isomerides, and for the 1-amino-8-naphthol- 34,1 kilos of diazotized 1-amino-8-li'ydroxl-sulfonic acid l-amino-8 hydroxynaphthaynaphthalene-3.6-disulfonic acid. After lens-3.6-disulfonic acid or 1-amino-8hydroxthe coupling is complete, an acetic acid '50- ynaphthalene-4.6-disulfonic acid. lution of 13,8 kilos of l-nitro-1-diazobenzene For the p-nitraniline may be substituledniis run'into the mass, and after the coupling nitraniline, 1n-ni'tro-p-toluidine, 4-chl0ro-2- is complete, it is salted out in the usual anisidine or the like in which cases there are manner. also obtained Valuable dyestuffs for dyeing A dyestutl is obtained with a good yield leather. v which dyes leather tanned with a Vegetable 1 ,1 a ent or with chromium deep chocolate 15 .Z. Dark-prawn forlcatlzcnl I [gown tints. v

19,9 kilos of p1cram1c acid are diazotized The dyestutl has the following formula: in the usual manner and coupled on om on on N ==N on N02 I =N on moss 0am Q I claim: azodyestufls according to the following -1. The process of produclng brown trlsscheme: azodyestufi's consisting in synthesizing trisn amine a resorclnol an aminonaphthol l anamina,

-40 2. The process of producing browntrisdiazonaphtholsulfonic acid, and then .unitazodyestufi's, H Ilg 111 c p ng wlth a mg a further diazo compound with the di'sresorcinol a diazo compound and a d azo azo dyestuff thus obtained. Iv naphthol, and then uniting a further dlazo 5. The process of pro'ducing brown trisazo com ound v with the .dlsazo dyestufi thus dyestuffs, consisting in coupling witha reobtamed. sorcinol a diazobenzenesulfonic acid and a 6'0 7 compound with the disazo dyestutf thus ob 3. The process of producing brown trisazo dyestuffs consisting in coupl ng with a resorcinol a diazotized aniline and a .diazo- I naphthol, and then uniting afurther diazo' diazonaphthol, and then uniting a diazo" benzenewith the di's'azo dyestufi' thus ob tained. v i f 6. The process of producing brown'tri'sa'zq dyestuffs, consisting in coupling with a re sorcinol a diazobenzencsulfonic 'acid and a diazonaphtholsulfonic acid, and uniting a diazobenzene with the disazo dyestufi thus obtained.

tained.

4. The process of producing brown trisazo dyestuflz's, consisting in coupling with a resorcinol a diazobenzene sulfonic acid and a in water, also soluble in concentrated sul- 7. The process of producing brown trisazo nitrodiazobenzene with the disazo dyestufi dyestuffs, consisting in coupling with a rethus obtained. sorcinol a diazobenzenesulfonic acid and a 8. As new products, the trisazo dyestuffs diazonaphtholsulfonic acid, and uniting a of the scheme diazotized amine aresorcinol an aminonaphthol an amine,

being dark-brown powders, readily soluble in water, also soluble in-concentrated sulfuric acid with a dark-brown color, insoluble in most of the organic solvents, dyeing leather from an acid bath dark brown tints.

9. As new products, the trisazo dyestuffs of the following formula:

R N:NR -N:N'R N:NR R and R, designating an aromatic residue,

ON=NResorcinolN=N- aminonaphtholsnllonic I acid-N=N substituted benzene or substituted benzene a homologue thereof or naphthalene being dark brown powders, readily soluble leather from an acid bath dark-brown tints. 11. As new products the disazo dyestuffs furic acid with a dark-brown color, insolof the following formula:

uble in most of the organic solvents, dyeing N=N-amlnonaphtholsulfonic acid-N=NO substituted benzene v Benzenesulionic acid or naphthalene.

owders, readily soluble leather from an acid bath dark-brown tints. In testimony whereof, I aflix my signature.

BARTHOLOMAUS- VOSSEN.

being dark-brown in water, also solu 1e in concentrated sulfuric acid with a dark-brown color, insoluble in most of the organic solvents, dyeing 

